Limitations of Preferential Enrichment: A Case Study on Tryptophan Ethyl Ester Hydrochloride

Since eutomer and distomer show different biological effects, access to pure enantiomers is essential. Preferential enrichment is a relatively new process of chiral resolution developed in the 90s. Extension of its scope was attempted with tryptophan ethyl ester hydrochloride. This salt meets one of the most important requirements for preferential enrichment, namely, a larger solubility for the pure enantiomers with reference to the racemic compound. But, due to the absence of a solid solution, this salt cannot perform preferential enrichment. This impossibility was endorsed by semi‐empirical molecular modeling.     

How Mixing and Light Heterogeneity Impact the Overall Growth Rate in Photobioreactors

The microalgae growth rate in photobioreactors responds with inertia to light stimuli. Here, light variations experienced by the algae are accessed through a coupling of an irradiance field calculation and a Lagrangian particle tracking. The response of algae to fluctuating light is then described by a relaxation model involving a single time constant, the value of which is identified from published data. The overall growth rate is calculated as the sum of individual growth rates of all particles. Instantaneous adaptation and full integration asymptotic behaviors are recovered whilst a finite time constant reveals that the overall growth rate is dependent both on mixing and light distribution. This methodology thus quantitatively relates the design parameters to the photobioreactor performance.     

Alumina foam catalyst supports for industrial steam reforming processes

The manufacture and the characterisation of alumina foams as alternative catalysts supports for industrial steam reforming processes are presented here. The possibility of use of alumina foams as catalysts supports in such processes is evaluated by studying their resistance toward mechanical and chemical stresses. The alumina foams produced are characterised owing to their processing parameters (slurry infiltration, sintering temperature, template pore size). Their ability to work in hydrothermal atmosphere is assessed by characterising the evolution of microstructures and mechanical strengths upon aging. Thermodynamic studies of the stability of alumina in industrial steam reforming working conditions are performed and correlated to the experiments to demonstrate the stability of such a system.     

NMR of insensitive nuclei enhanced by dynamic nuclear polarization

Despite the powerful spectroscopic information it provides, Nuclear Magnetic Resonance (NMR) spectroscopy suffers from a lack of sensitivity, especially when dealing with nuclei other than protons. Even though NMR can be applied in a straightforward manner when dealing with abundant protons of organic molecules, it is very challenging to address biomolecules in low concentration and/or many other nuclei of the periodic table that do not provide as intense signals as protons. Dynamic Nuclear Polarization (DNP) is an important technique that provides a way to dramatically increase signal intensities in NMR. It consists in transferring the very high electron spin polarization of paramagnetic centers (usually at low temperature) to the surrounding nuclear spins with appropriate microwave irradiation. DNP can lead to an enhancement of the nuclear spin polarization by up to four orders of magnitude. We present in this article some basic concepts of DNP, describe the DNP apparatus at EPFL, and illustrate the interest of the technique for chemical applications by reporting recent measurements of the kinetics of complexation of 89Y by the DOTAM ligand.     

Iron oxide magnetic nanoparticles used as probing agents to study the nanostructure of mixed self-assembled monolayers

Self-assembled monolayers (SAMs) of organic molecules are of exceptional technological importance since they represent a convenient, flexible, and simple system for tuning the chemical and physical properties of surfaces. The fine control of surface properties is directly dependent on the structure of mixed SAMs which is difficult to characterize at the nanoscale with usual techniques such as scanning probe microscopies. In this study, we report on a general method to investigate at the nanoscale the structure of molecular patterns which consist in SAMs of two components. Iron oxide nanoparticles (NPs) have been used as probing agents to study indirectly the structure of mixed SAMs. Mixed SAMs were prepared by the replacement of mercaptododecane (MDD) adsorbed by mercaptoundecanoic acid (MUA) molecules on gold substrates. Therefore, the SAM surface displays both chelating carboxylic terminal groups and non-chelating methylene terminal groups. As NPs have been previously demonstrated to specifically interact with carboxylic acid groups, the increasing density in NPs was correlated with the evolution of the COOH/CH(3) terminal groups ratio. Therefore the structure of mixed SAMs was studied indirectly as well as the kinetic of the replacement reaction and its mechanism. With this aim, we took advantage of the SPR properties of the gold substrate and of the high refractive index of iron oxide nanoparticles to follow their assembling on mixed SAMs as a time resolved study. The high sensitivity and tuning of the SPR signal over a wide range of wavelengths are correlated with the NP density. Furthermore, SEM combined with image analysis has allowed studying the replacement rate of MDD by MUA in SAMs. We took also advantages of the magnetic properties of NPs to evaluate qualitatively the replacement of thiol molecules.     

Synthesis and Surface-Active Properties of Uronic Amide Derivatives,Surfactants from Renewable Organic Raw Materials

Short chemical syntheses were developed to produce a new set of surfactants from uronic acids derived from widely available raw materials. Three different strategies were used to synthesize uronic amide derivatives, the structures of which were totally characterized by spectrometric methods (IR, MS, ¹H-RMN and ¹³C-RMN). The best one, using an acid chloride as the synthetic intermediate, furnished the expected amides as a mixture of anomers in 46–58% global yield. Surface-active properties (CMC, γ_cmc, Γ_max, A _min) of homologous series of uronic acid N-alkylamides from C8 to C18 were also assessed. In general, these sugar-based surfactants exhibited good surface-activities, and appeared as valuable nonionic surfactants compared to octylphenol 9–10 ethylene oxide condensate, the most well-known nonionic surfactant. Increasing the alkyl chain length influenced the CMC values for both glucuronic and galacturonic N-alkylamide derivatives. The galacturonic N-alkylamides decreased γ_cmc at slower values than their counterpart’s glucuronic N-alkylamides.     

Electrochemical and spectroscopic characterization of lithium titanate spinel Li4Ti5O12

Herein we describe electrochemical and spectroscopic properties of lithium titanate spinel as well as an easy method based on colorimetry to determine the lithium content of electrodes containing lithium titanate spinel as active material. Raman microspectrometry measurements have been performed to follow lithium insertion into and extraction from the active material, respectively. The Raman signals display a pronounced fading of intensity already at low levels of lithium intercalation and disappear at a SOC higher than ∼10%. However, the colorimetric method can be used up to a SOC of 50%.     

Extrusion of Nanocellulose‐Reinforced Nanocomposites Using the Dispersed Nano‐Objects Protective Encapsulation (DOPE) Process

Cross‐linked alginate capsules a few millimeters in diameter have been formed by immersion in a CaCl₂ solution. When adding cellulose whiskers or microfibrillated cellulose to the aqueous alginate solution, nanocomposite capsules containing 40 wt.% cellulosic nanoparticles were obtained. The morphology and compression strength of these capsules were investigated by microscopic observations and crushing tests, respectively. The capsules were extruded with a thermoplastic polymer. Visual inspection of the ensuing films shows a nonhomogeneous dispersion of the capsules that kept their integrity after extrusion. It results in preliminary disappointing mechanical properties of the composite films. However, further investigation is in progress to optimize this simple and ecofriendly process.

     

Effect of processing procedures and conditions on structural,morphological, and rheological properties of polyethylene/polyamide/nanoclay blends

The article deals with the effect of processing procedures and conditions on structural, morphological, and rheological properties of ternary blends composed of polyethylene (PE), polyamide (PA)‐12, and organically modified montmorillonite nanoclay with selective affinity. Samples were prepared from PE/PA and PA/PE blends, either by simultaneous mixing or from a polymer/clay masterbatch, using two processing conditions. The results have shown the existence of a weight fraction threshold, above which no significant processing effect was observed. Below this weight fraction threshold, the results tend to underline the significant role of two parameters that depend on processing procedures and/or conditions: the contact time between PE and PA phases and the contact time between clay and PA. Clay structure, blend morphology, and rheological properties were all shown to depend on these two parameters, and also on the nature of the matrix (PE or PA), because of the selective affinity of clay toward polymer phases. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Influence of Ammonium Pentaborate (APB) on the Performance of Urea Formaldehyde (UF) Adhesives for Plywood

Ammonium pentaborate (APB) was used to modify urea formaldehyde (UF) resins, in which the formaldehyde to urea molar ratio was set at 1.80, 1.50, 1.25, and 1.05. Some specific properties, including gel time, free formaldehyde content in UF, bond strength, and formaldehyde emission levels from plywood were evaluated. The result showed that APB increased the gel time length, but also decreased free formaldehyde content and emission levels, which was reduced mostly by 79.0% and 81.4%, respectively. The result of bond strength indicated that APB was proper to modify high F/U molar ratio of UF resin regardless of the loading level, but a recommended loading level should be considered to relevantly lower the F/U molar ratio of UF. The suggested loading level of APB to UF is 8.0% to 6.0%, 6.0%, and 4.0% to UF resin with F/U molar ratio of 1.8, 1.5, and 1.25 separately.